CN110423320A - A kind of DOPO polybenzoxazine containing list of good flame resistance and preparation method thereof - Google Patents
A kind of DOPO polybenzoxazine containing list of good flame resistance and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
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Abstract
The invention discloses DOPO polybenzoxazines containing list of a kind of good flame resistance and preparation method thereof, it is using bisphenol-A and the benzoxazine of aniline synthesis as raw material, it is phenol source that bisphenol-A of the synthesis containing single DOPO is reacted with DOPO, it is amine source using polyetheramine and isocyanates as the amine terminated polyether urea of Material synthesis, the polyethers urea type benzoxazine of the DOPO containing list of good flame resistance is prepared by Mannich reaction.The present invention introduces flexible group and DOPO molecule by upper in benzoxazine monomer, makes it have extraordinary anti-flammability, and material flexibility also preferably can have extraordinary application prospect.
Description
Technical field
The invention belongs to polymeric material fields, and in particular to a kind of DOPO polybenzoxazine containing list of good flame resistance and its
Preparation method.
Background technique
Polybenzoxazine is a kind of novel thermosetting phenolic resin, has many excellent performances, such as mechanical performance
And good in thermal property, water imbibition, dielectric constant and surface free energy are low, can the ring-opening polymerisation under heating or catalyst action,
Without volume contraction etc. after polymerization, at present in rubber, coating, adhesive, microelectronics and resin transfer moulding (RTM) processing etc.
Multiple fields receive significant attention.
Single polybenzoxazine poor processability, brittleness is big, and flame retardant property is inadequate, these defects, which limit it, to be made
With.For the application range for widening polybenzoxazine, research is usually modified to it, to improve its processing performance or improve its resistance
Fire performance, toughness, hot property and mechanical performance etc..The modification of polybenzoxazine is specifically included that answers according to the reality of different occasions
With needs, using the strong advantage of MOLECULE DESIGN, synthesizing new polybenzoxazine or strand contain benzoxazine class formation
Material, or the method by being blended or being copolymerized introduce other components in benzoxazine matrix, to improve polybenzoxazine tree
Lipid energy.As novel hot setting resin, improves the performances such as anti-flammability and the toughness of polybenzoxazine and led for expanding its application
Domain has a very important significance.Therefore, flame retardant property is good and the polybenzoxazine of toughness improvement is significantly for research.
In polymer arts, the fire retardant containing N, P element just gradually replaces halogen fire retardant, and DOPO is a kind of novel
Flame retardant intermediate, and the P-H key in DOPO has extraordinary activity, and it is anti-chemistry can to occur with some active groups
It answers.Due to N rich in DOPO, P element, introducing DOPO group in a polymer matrix can be improved the anti-flammability of material
Energy.And flexible group is introduced in polybenzoxazine matrix can significantly improve the flexibility of material.
Lin C.H.[Journal of Polymer Science Part A-polymer Chemistry,2010,48,
4555-4566] etc. utilize three kinds of distinct fragrance race diamines, three kinds of fragrant phosphorous benzoxazines of amine type are prepared for by one-step method,
As a result these materials thermal stability with higher and preferable flame-retarding characteristic are proved.Xu G.[Journal of Applied
Polymer Science, 2015,132:41634-41644] two different benzoxazines containing DOPO etc. have been synthesized, and have been ground
Study carefully the characteristic of itself and graphene oxide compound, as a result proves the limit oxygen of two kinds of polybenzoxazines containing DOPO prepared by it
Index significantly improves, and the flame retardant property of material improves.Sponto′n M.[Polymer Degradation and
2009,94 (10): Stability 1693-1699] etc. has synthesized the benzoxazine containing DOPO, result verification material by three-step approach
Material has extraordinary flame-retarding characteristic.Agag T. [Macromolecules, 2010,43,7122-7127] etc. has synthesized a system
Column low viscosity polyether-based main chain benzoxazine, and its polymer is flexible.Liu Y.[Reactive and
Functional Polymers, 2016,102:62-69] etc. synthesis five kinds of difunctional polyether-based benzoxazines and study its shape
Shape memory function.
DOPO molecule is introduced in benzoxazine monomer can improve the flame retardant property of polymer, and the introducing of flexible group
It can be obviously improved the flexibility of polymer, facilitate the application field for widening polybenzoxazine.
Summary of the invention
Aiming at the shortcomings existing in the above problems, the present invention provides a kind of polyphenyl of the DOPO containing list of good flame resistance simultaneously
Oxazines and preparation method thereof, it is intended to improve the anti-flammability and flexibility of polybenzoxazine.
The present invention is to realize goal of the invention, is adopted the following technical scheme that
The invention discloses a kind of DOPO polybenzoxazines containing list of good flame resistance, shown in structural formula such as formula (1):
In formula (1), R1Structure such as formula (a) or formula (b) shown in, R2Structure such as formula (c), formula (d) or formula (e) shown in:
The invention also discloses the preparation methods containing single DOPO polybenzoxazine of the good flame resistance, including walk as follows
It is rapid:
Step 1, by aniline and paraformaldehyde dissolution in a solvent, 0~10 DEG C low-temp reaction 0.5~2 hour, be then added
Bisphenol-A is simultaneously warming up to 40~100 DEG C, is stirred to react 4-15 hours, and the solution of benzoxazine monomer, the benzoxazine list is made
Shown in the structure of body such as formula (2):
DOPO is added in the solution of step 1 gained benzoxazine monomer in step 2, then under inert gas protection, in
20~100 DEG C are reacted 2~10 hours, obtain the bisphenol-A solution containing single DOPO, the structural formula of the bisphenol-A containing single DOPO is such as
Shown in formula (3):
Step 3 dissolves polyetheramine and isocyanates in a solvent, then reacts 2~6 hours, obtains at 40~100 DEG C
Amine terminated polyether urea solution, shown in the structural formula such as formula (4) of the amine terminated polyether urea:
Step 4 is added paraformaldehyde and is dissolved in step 3 gained amine terminated polyether urea solution, anti-in 0~10 DEG C of low temperature
It answers 0.5~2 hour, the bisphenol-A solution containing single DOPO obtained by step 2 is then added, and be warming up to 40~100 DEG C, is stirred to react
4-15 hours, separation, purifying obtained the benzoxazine monomer containing single DOPO, shown in structural formula such as formula (5):
Step 5 carries out elevated cure to the benzoxazine monomer containing single DOPO, i.e. acquisition target product DOPO containing list
Polybenzoxazine.
Further: in step 1, bisphenol-A is 1:2:4 with the amount of aniline and the substance of paraformaldehyde proportion；In step 2,
The amount proportion of DOPO and the substance of bisphenol-A in step 1 are 1:1；In step 3, isocyanic acid in amido and isocyanates in polyetheramine
The amount proportion of the substance of root is 2:1；In step 4, phenolic hydroxyl group in the bisphenol-A containing single DOPO, the Amino End Group in amine terminated polyether urea
Amount proportion with the substance of paraformaldehyde is 1:1:2.
Further, step 1 is independently selected from solvent described in step 3 as ethyl alcohol, acetone, chloroform, two
Chloromethanes, tetrahydrofuran or N, N-dimethylformamide.
Further, in step 3, the polyetheramine be D230, D400, D2000, ED600, ED900, ED2000, it is described
Isocyanates is 4,4- methyl diphenylene diisocyanate (MDI), toluene di-isocyanate(TDI) (TDI) or isophorone diisocyanate
Ester (IPDI).When polyetheramine is D230, D400, D2000, R1Structure such as formula (a) shown in；When polyetheramine be ED600,
When ED900, ED2000, R1Structure such as formula (b) shown in.The value of x, y, z is by specific selected polyetheramine in formula (a) and formula (b)
Depending on.
Further, elevated cure described in step 5 is that 2~10 temperature ladders are arranged within the temperature range of 80~200 DEG C
Degree, each temperature gradient retention time are 1~4 hour.
Compared with prior art, the invention has the benefit that
The invention discloses a kind of DOPO polybenzoxazines containing list, are introduced by upper in benzoxazine monomer containing abundant
N, P element DOPO molecule, make it have extraordinary flame retardant property, simultaneously because in monomer flexible group introducing, make
Obtaining material also has extraordinary flexibility, is greatly broadened the application range of polybenzoxazine, before having extraordinary application
Scape.
Detailed description of the invention
Fig. 1 is the synthetic route chart of the invention containing single DOPO polybenzoxazine；
Fig. 2 is the hydrogen nuclear magnetic spectrogram of the benzoxazine monomer containing single DOPO synthesized in embodiment 1；
Fig. 3 is different phase of the benzoxazine monomer containing single DOPO in elevated cure in embodiment 1, Fu of products therefrom
In leaf infrared spectrum；
Fig. 4 is the bending property photo containing single DOPO polybenzoxazine sample obtained by embodiment 1, and wherein a is sample
Photo before bending, b are the bending photo of sample, and c is that sample bent test terminates the photo after 30s.
Fig. 5 is the pole containing single DOPO polybenzoxazine sample and without DOPO polybenzoxazine obtained in embodiment 1
Limited oxygen index test result.
Specific embodiment
It elaborates below to the embodiment of the present invention, the present embodiment carries out under the premise of the technical scheme of the present invention
Implement, the detailed implementation method and specific operation process are given, but protection scope of the present invention is not limited to following implementation
Example.
Embodiment 1
The present embodiment polybenzoxazine containing DOPO synthesizes as follows:
1.86g aniline and 1.2g paraformaldehyde are dissolved in 200mL dehydrated alcohol by step 1,5 DEG C react 1 hour, so
2.28g bisphenol-A is added afterwards and is warming up to 80 DEG C, is stirred to react 10 hours, the solution of benzoxazine monomer is made.
2.16g DOPO is added in step 2 in the solution of step 1 gained benzoxazine monomer, then under nitrogen protection,
Continue 80 DEG C to be stirred to react 7 hours, obtains the bisphenol-A solution containing single DOPO.
Step 3, that 6g polyetheramine ED600 and 1.25g 4,4- methyl diphenylene diisocyanate is dissolved in 100mL is anhydrous
It in ethyl alcohol, is then stirred to react at 40 DEG C 2 hours, obtains amine terminated polyether urea solution.
0.6g paraformaldehyde is added in step 3 gained amine terminated polyether urea solution, and is kept for 5 DEG C and is stirred to react for step 4
1 hour, then the bisphenol-A solution containing single DOPO obtained by step 2 is added thereto, and be warming up to 80 DEG C, it is small to be persistently stirred to react 6
When, it is after reaction transparent orange solution.After solution is cooling, solvent is evaporated completely, products therefrom chloroform is molten
Xie Hou is cleaned 3 times with the sodium hydroxide solution of 1mol/L, then is washed with deionized several times until solution is neutral,
Chloroform in solution is finally evaporated to clean, benzoxazine monomer of the acquisition containing single DOPO again.
Step 5 carries out elevated cure to the benzoxazine monomer containing single DOPO, i.e. acquisition target product DOPO polyphenyl containing list
And oxazines, elevated cure are carried out with 20 DEG C of temperature gradient within the temperature range of 80~200 DEG C, are opened under each temperature gradient
Cyclopolymerization 1.5 hours, i.e., solidify 1.5 hours respectively in 80 DEG C, 100 DEG C, 120 DEG C, 140 DEG C, 160 DEG C, 180 DEG C, 200 DEG C.
Fig. 2 is the hydrogen nuclear magnetic spectrogram of the benzoxazine monomer containing single DOPO synthesized in the present embodiment.It can from figure
Out, solvent carbon deuterium chloride CDCl3Chemical shift be δ=7.23ppm；It is-CH positioned at δ=0.8~2.0ppm3Group proton peak；
Chemical shift δ=3.6ppm corresponds to the-O-CH in fat chain structure2Group proton peak；Chemical shift δ=3.77ppm is indicated
- the CH being connected with phenyl ring2The proton peak of-N- hydrogen belongs to-N-CH at δ=4.00ppm2- CH in-P- group2Middle Hydrogen Proton peak；
Belong to proton peak on the monomer phenyl ring of benzoxazine containing DOPO between δ=6.5~7.5ppm multiple resonance state；Chemical shift in δ=
Characteristic peak at 4.55ppm and δ=5.30ppm respectively with-Ar-CH in oxazines2- N- and-O-CH2- N group proton is related, verifying
The oxazines ring structure of benzoxazine.
Fig. 3 is the FTIR of the sample after different temperatures solidifies of the benzoxazine monomer containing single DOPO in the present embodiment step 5
Spectrogram.It can be seen from the figure that all samples not only occur being located at 1102cm-1Absorption peak, this, which belongs in polyether chain, opposes
Claim C-O-C stretching vibration peak, and in 2770~3020cm-1Between there is stronger and wide peak, this belongs in polyether backbone-
CH2Antisymmetric stretching vibration peak, while in 1237cm-1There is the characteristic absorption peak of P=O in position；It is present in 676 in monomer
And 1301cm-1The absorption peak of position corresponds respectively to antisymmetry C-O-C stretching vibration peak in substituted benzene ring and oxazines ring, with solid
Change the raising of temperature, intensity gradually weakens (or even disappearance), shows benzoxazine ring-opening polymerisation and obtain polybenzoxazine, position
In 1606 and 1685cm-1Locating peak is that 1,2,3,5 phenyl ring four replace absorption peak, is increased with temperature, peak intensity also gradually dies down even
It disappears, this is mainly due to caused by benzene ring substitution group quantity increase；And it is located at 939cm-1The oxazines ring characteristic absorption peak of position,
Variation tendency is unobvious in temperature-rise period, this may be because its with caused by P-O-C overlap of peaks.
Nucleus magnetic hydrogen spectrum and infrared spectrum result demonstrate the successful preparation containing single DOPO benzoxazine monomer and its polymer.
Fig. 4 is the bending property test comparison picture of the polybenzoxazine containing DOPO obtained by the present embodiment, and wherein a is sample
Photo before product bending, b are the bending photo of sample, and c is that sample bent test terminates the photo after 30s.It can be clear from photo
Find out to Chu that this sample has extraordinary flexibility, biggish bending may be implemented in sample, although and sample after external force cancellation
It can not achieve complete recovery, but can restore to a certain extent.
Fig. 5 is the DOPO polybenzoxazine sample containing list obtained by the present embodiment and is free of DOPO polybenzoxazine sample
(synthesis mode without DOPO polybenzoxazine control sample is identical as polybenzoxazine containing DOPO herein, only without step
Bisphenol-A is only selected in rapid one, step 2, phenol source) limit oxygen index measurement result.The limit oxygen index measurement result of multiple sample
It has been shown that, the limit oxygen index of the polybenzoxazine without DOPO are 18.5%, belong to combustible material, and the DOPO polyphenyl containing list and are disliked
The limit oxygen index of piperazine is 28.5%, belongs to nonflammable material, the flame-retarding characteristic of material significantly improves.
Embodiment 2
The present embodiment DOPO polybenzoxazine containing list synthesizes as follows:
1.86g aniline and 1.2g paraformaldehyde are dissolved in 200mL dehydrated alcohol by step 1, are reacted 1 hour at 5 DEG C,
Then 2.28g bisphenol-A is added and is warming up to 80 DEG C, is stirred to react 10 hours, the solution of benzoxazine monomer is made.
2.16g DOPO is added in step 2 in the solution of step 1 gained benzoxazine monomer, then under protection of argon gas,
It is continuously heating to 80 DEG C to be stirred to react 7 hours, obtains the bisphenol-A solution containing single DOPO.
6g polyetheramine ED600 and 0.87g toluene di-isocyanate(TDI) is dissolved in 200mL dehydrated alcohol by step 3, then
It is stirred to react at 50 °C 2 hours, obtains amine terminated polyether urea solution.
Step 4 is added 0.6g paraformaldehyde and is dissolved in step 3 gained amine terminated polyether urea solution, at a temperature of 5 DEG C
It is stirred to react 1 hour, the bisphenol-A solution containing single DOPO obtained by step 2 is then added, is warming up to 80 DEG C, and continue to be stirred to react 6
Hour, it is after reaction transparent orange solution.After solution is cooling, solvent is evaporated to clean, products therefrom chloroform
It after dissolution, is cleaned 3 times, then is washed with deionized several times until solution is that neutrality is with the sodium hydroxide solution of 1mol/L
Only, chloroform in solution is finally evaporated to clean, benzoxazine monomer of the acquisition containing single DOPO again.
Step 5 carries out elevated cure to the benzoxazine monomer containing single DOPO, i.e. acquisition target product DOPO polyphenyl containing list
And oxazines, elevated cure are carried out with 20 DEG C of temperature gradient within the temperature range of 80~200 DEG C, are opened under each temperature gradient
Cyclopolymerization 1.5 hours, i.e., solidify 1.5 hours respectively in 80 DEG C, 100 DEG C, 120 DEG C, 140 DEG C, 160 DEG C, 180 DEG C, 200 DEG C.
It is tested through analysis, the present embodiment products therefrom is target product, and equally has extraordinary flame retardant property and soft
Toughness.
Embodiment 3
The present embodiment DOPO polybenzoxazine containing list synthesizes as follows:
1.86g aniline and 1.2g paraformaldehyde are dissolved in 200mL dehydrated alcohol by step 1, are reacted 1 hour at 5 DEG C,
Then 2.28g bisphenol-A is added and is warming up to 80 DEG C, is stirred to react 10 hours, the solution of benzoxazine monomer is made.
2.16g DOPO is added in step 2 in the solution of step 1 gained benzoxazine monomer, then under nitrogen protection,
It is warming up to 80 DEG C to continue to be stirred to react 7 hours, obtains the bisphenol-A solution containing single DOPO.
4g polyetheramine D400 and 1.25g 4,4- methyl diphenylene diisocyanate is dissolved in the anhydrous second of 100mL by step 3
It in alcohol, is then stirred to react at 70 DEG C 2 hours, obtains amine terminated polyether urea solution.
0.6g paraformaldehyde and stirring and dissolving is added in step 4 in step 3 gained amine terminated polyether urea solution, in 5 DEG C of temperature
It is stirred to react under degree 1 hour, the bisphenol-A solution containing single DOPO obtained by step 2 is then added, is warming up to 80 DEG C, it is anti-to continue stirring
It answers 10 hours, is after reaction transparent orange solution.After solution is cooling, solvent is evaporated to clean, products therefrom trichlorine
It after methane dissolution, is cleaned 3 times, then is washed with deionized several times until solution is neutrality with the sodium hydroxide solution of 1mol/L
Until, chloroform in solution is finally evaporated to clean, benzoxazine monomer of the acquisition containing single DOPO again.
Step 5 carries out elevated cure to the benzoxazine monomer containing single DOPO, i.e. acquisition target product DOPO polyphenyl containing list
And oxazines, elevated cure are carried out with 20 DEG C of temperature gradient within the temperature range of 80~200 DEG C, are opened under each temperature gradient
Cyclopolymerization 1.5 hours, i.e., solidify 1.5 hours respectively in 80 DEG C, 100 DEG C, 120 DEG C, 140 DEG C, 160 DEG C, 180 DEG C, 200 DEG C.
It is tested through analysis, the present embodiment products therefrom is target product, and equally has extraordinary flame retardant property and soft
Toughness.
Embodiment 4
The present embodiment DOPO polybenzoxazine containing list synthesizes as follows:
1.86g aniline and 1.2g paraformaldehyde are dissolved in 200mL dehydrated alcohol by step 1, react 1 at a temperature of 5 DEG C
Hour, 2.28g bisphenol-A is then added and is warming up to 80 DEG C, is stirred to react 10 hours, the solution of benzoxazine monomer is made.
2.16g DOPO is added in step 2 in the solution of step 1 gained benzoxazine monomer, then under protection of argon gas,
Continue 80 DEG C to be stirred to react 7 hours, obtains the bisphenol-A solution containing single DOPO.
9g polyetheramine ED900 and 1.11g isophorone diisocyanate is dissolved in 100mL dehydrated alcohol by step 3,
Then it is stirred to react at 70 DEG C 2 hours, obtains amine terminated polyether urea solution.
Step 4 is added 0.6 paraformaldehyde in step 3 gained amine terminated polyether urea solution and stirs, at a temperature of 5 DEG C
It is stirred to react 1 hour, the bisphenol-A solution containing single DOPO obtained by step 2 is then added, is warming up to 80 DEG C, and continue to be stirred to react 8
Hour, it is after reaction transparent orange solution.After solution is cooling, solvent is evaporated to clean, products therefrom chloroform
It after dissolution, is cleaned 3 times, then is washed with deionized several times until solution is that neutrality is with the sodium hydroxide solution of 1mol/L
Only, chloroform in solution is finally evaporated to clean, benzoxazine monomer of the acquisition containing single DOPO again.
Step 5 carries out elevated cure to the benzoxazine monomer containing single DOPO, i.e. acquisition target product DOPO polyphenyl containing list
And oxazines, elevated cure are carried out with 20 DEG C of temperature gradient within the temperature range of 80~200 DEG C, are opened under each temperature gradient
Cyclopolymerization 1.5 hours, i.e., solidify 1.5 hours respectively in 80 DEG C, 100 DEG C, 120 DEG C, 140 DEG C, 160 DEG C, 180 DEG C, 200 DEG C.
It is tested through analysis, the present embodiment products therefrom is target product, and equally has extraordinary anti-flammability and flexible
Property.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (6)
1. a kind of DOPO polybenzoxazine containing list of good flame resistance, it is characterised in that:
Shown in the structural formula such as formula (1) containing single DOPO polybenzoxazine:
In formula (1), R1Structure such as formula (a) or formula (b) shown in, R2Structure such as formula (c), formula (d) or formula (e) shown in:
2. a kind of preparation method containing single DOPO polybenzoxazine of good flame resistance described in claim 1, which is characterized in that including
Following steps:
Step 1, by aniline and paraformaldehyde dissolution in a solvent, 0~10 DEG C low-temp reaction 0.5~2 hour, bis-phenol is then added
A is simultaneously warming up to 40~100 DEG C, is stirred to react 4-15 hours, and the solution of benzoxazine monomer is made, the benzoxazine monomer
Shown in structure such as formula (2):
DOPO is added in the solution of step 1 gained benzoxazine monomer in step 2, then under inert gas protection, in 20~
100 DEG C are reacted 2~10 hours, and the bisphenol-A solution containing single DOPO, the structural formula such as formula (3) of the bisphenol-A containing single DOPO are obtained
It is shown:
Step 3 dissolves polyetheramine and isocyanates in a solvent, then reacts 2~6 hours at 40~100 DEG C, obtains end ammonia
Base polyethers urea solution, shown in the structural formula such as formula (4) of the amine terminated polyether urea:
Step 4 is added paraformaldehyde and is dissolved in step 3 gained amine terminated polyether urea solution, in 0~10 DEG C of low-temp reaction
0.5~2 hour, the bisphenol-A solution containing single DOPO obtained by step 2 is then added, and be warming up to 40~100 DEG C, is stirred to react 4-
15 hours, separation, purifying obtained the benzoxazine monomer containing single DOPO, shown in structural formula such as formula (5):
Step 5 carries out elevated cure to the benzoxazine monomer containing single DOPO, i.e. acquisition target product DOPO polyphenyl containing list
And oxazines.
3. preparation method according to claim 2, it is characterised in that:
In step 1, bisphenol-A is 1:2:4 with the amount of aniline and the substance of paraformaldehyde proportion；
In step 2, the amount proportion of DOPO and the substance of bisphenol-A in step 1 are 1:1；
In step 3, the amount proportion of the substance of isocyano is 2:1 in amido and isocyanates in polyetheramine；
In step 4, the substance of phenolic hydroxyl group, the Amino End Group in amine terminated polyether urea and paraformaldehyde in the bisphenol-A containing single DOPO
Amount proportion is 1:1:2.
4. preparation method according to claim 2, it is characterised in that:
Solvent described in step 1 and step 3 is independently selected from as ethyl alcohol, acetone, chloroform, methylene chloride, tetrahydro furan
It mutters or N, N-dimethylformamide.
5. preparation method according to claim 2, it is characterised in that:
In step 3, the polyetheramine is D230, D400, D2000, ED600, ED900, ED2000, and the isocyanates is 4,4-
Methyl diphenylene diisocyanate, toluene di-isocyanate(TDI) or isophorone diisocyanate.
6. preparation method according to claim 2, it is characterised in that: elevated cure described in step 5 is at 80~200 DEG C
In temperature range, 2~10 temperature gradients are set, each temperature gradient retention time is 1~4 hour.
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| CN104193967A (en) * | 2014-09-05 | 2014-12-10 | 史铁钧 | DOPO-containing bisphenol A-monobenzoxazine/epoxy resin copolymer and preparation method thereof |
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| CN101824146A (en) * | 2010-04-15 | 2010-09-08 | 华烁科技股份有限公司 | Preparation method of bisphenol A benzoxazine resin with high stability |
| CN102093556A (en) * | 2011-01-19 | 2011-06-15 | 华东理工大学 | Preparation method of low viscosity benzoxazine |
| CN104193967A (en) * | 2014-09-05 | 2014-12-10 | 史铁钧 | DOPO-containing bisphenol A-monobenzoxazine/epoxy resin copolymer and preparation method thereof |
| CN105968350A (en) * | 2016-05-24 | 2016-09-28 | 合肥工业大学 | High-toughness polyether urea benzoxazine resin and preparation method thereof |
Cited By (2)
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| CN111825875A (en) * | 2020-07-25 | 2020-10-27 | 周有松 | Toughened benzoxazine foamed board and preparation method thereof |
| CN111825875B (en) * | 2020-07-25 | 2023-01-20 | 周有松 | Toughened benzoxazine foamed plate and preparation method thereof |
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